Process of producing chlorinated ethers



Patented May 6, 1941 PROCESS OF lRODUCING CHLORINATED ETHERS Heinrich Hopfi, Ludwigshafen on the Rhine,

Germany, assignor, by mesne assignments, to General Aniline, & -Film Corporation, New York,N. Y., a corporation of Delaware N Drawing. Application February 25, 1939, Se-

rial N0. 258,458. In Germany March 4, 1938 6 Claims. (:01. 260--611) The present invention relates to chlorinated ethers and a process of producing, same.

I have found that chlorinated ethers corre sponding to the general formula Bi A-C-OB wherein A stands for benzene or a naphthalene nucleus, R1 and R2 for hydrogen or chlorine or a beta-chloralkoxy group and B for a beta-- chloralkyl group, can be obtained by causing alkylene-oxides to react with compounds of "the wherein A stands for benzene or a naphthalene nucleus and R1 and R2 for hydrogen or chlorine.

The reaction, for instance if benzylchloride and ethyleneoxide are used as starting mate: rials, proceeds as follows: v y p CH2CI+CHTCHI -oHi-0-c11i.oHio1 As halogen compounds corresponding to the second formula mentioned above there may be mentioned for example benzylchloride, benzal chloride, benzo trichloride or alpha-chloralkylnaphthalenes.

Among olefine oxides there may be mentioned ethylene, propylene, butylene, phenylethylene and butadiene oxides.

The initial materials, in about equimolecular proportions, are heated in a closed vessel until the completion of the reaction, for example at from 100 to 200 C. The chlorine compound may also be heated to the reaction temperature, if desired after dilution with a solvent, the olefine oxide then being led in in the vapor state or allowed to drop in in the liquid state.

The reaction may be accelerated by catalysts, such as metallic copper, copper salts, small amounts of caustic alkalies, such as sodium or When starting from compounds having two or more chlorine atoms, the olefine oxide may enter into the molecule two or more times.

The following examples will further illustrate how the said invention may be carried out in practice but the invention is not restricted to these examples. The parts are by weight.

Example 1 1 26 parts of benzyl chloride, parts of ethyleneoxide and 0.5 part of cupric chloride are heated to 160 C. for 10 hours in a closed vessel. The mixture is then distilled under reduced general formula, pressure. There are obtained 130 parts of a R1 colorless oil having a pleasant odor which passes over between and C. under a pressure of 3 millimeters (mercury, gauge). According to R, analysis, which gives the formula C9H11OC1, and

. the course of the reaction, the product is benzylpotassium hydroxide, or organic bases, such as piperidine.

The reaction mixture is preferably worked up by distillation. The ethers containing chlorine obtained are, depending on the initial materials, from water-clear to pale yellowish oils having a pleasant odor or solid, salve-like substances.

omega-chlorethyl ether. There are also formed small amounts of an oil passing over between and 150 C. at 'a pressure of 2 millimeters (mercury gauge) in which a hydroxyethyl derivative of the said =chlorether is probably contained. v

By using the equivalent amount of propylene oxide instead of ethylene oxide, benzyl-chlorpropyl ether which boils at from to C. under a pressure of 3 millimeters (mercury gauge) is obtained.

Example 2 A mixture of 81 parts of benzal chloride and 45 parts of ethylene oxide is heated at 120 C. for 10 hours in a closed vessel. The reaction mix ture is then distilled under reduced pressure. 85 parts of a pale yellowish colored oil having a pleasant odor and boiling at from 120 to C. at a pressure of 2 millimeters (merciu'y gauge) are obtained; according to analysis and the course of the reaction it is:

o-orn-cmm con-0H OCH20H2C1 Propylene oxide may be reacted with benzal chloride in the same way.

Example 3 200 par-ts of benzotrichloride are heated to 100 C. with 50 parts of ethylene oxide for 10 hours. By working up in the abovementioned. manner, parts of an oil boiling between 95 and 105 C. under a pressure of 3 millimeters (mercury gauge) are obtained: it probably has the constitution:

Example 4 A mixture of 176 parts of omega-chlormethylnaphthalene and 45 parts of ethylene oxide is',

heated in a closed vessel at 150 C. for hours while stirring. The reaction product is thendis tilled under reduced pressure. There. are ob.-

tained 150 partsof an oil which passesover-be tween 190 and 200 C. under a pressureoi 2 mi11i-- 'meters (mercury gauge). According to analysis.

the new compound has the formula C10I'I1CH2OCH2.CH2.C1

What I claim is:

1. A process of producing chlorinated ethers which comprises heating compounds of the general formula wherein A stands for an aromatic radical selected from the class consisting of benzene and naphthalene, R1 and R2 for a member of the class consisting of hydrogen and chlorine, with alkylene-oxides. v

2. A process of producing chlorinated .ethers which comprises heating compounds of the general formula V I R1 I wherein A stands for an aromatic radical selected from the class consisting of benzene and naphthalene, R1 and R2 for a member ofthe class consisting. of hydrogen and chlorine, with alkyla caustic alkali as catalyst.

3. A process of producing chlorinated ethers which comprises heating compounds of the general formula R1 A-(J-Cl 7 1'1,

wherein A stands for an aromatic radical selectled from the class consisting of benzene and naphthalene, R1 and. R2 for a member of the class consisting of hydrogen and chlorine, with "alkyleneoxides in the presence of a copper salt.

The ether of the formula C-OCH2.CH2C1 being a colorless oil boiling at from to C. undera reduced pressure of 3 millimeters mercury gauge.

5. A chlorinated ether corresponding to the general formula which comprises heating compounds of the general formula:

R1 A-Ji-Cl l.

wherein A stands for an aromatic radical selected from the'class consisting of benzene and naphthalene, R1 and R2 for a member of the class consisting of hydrogen and chlorine, with alkylene oxides inthe presence of small amounts of a heterocyclic base as catalyst.

' HEINRICH HOPFF. 

